Structural Relaxation Mechanisms Research Articles

Epitaxial growth of GaInAsBi thin films on Si (001) substrate using pulsed laser deposition

The results of a comprehensive study of growing a Ga1-yInyAs1-xBix quaternary alloy on a Si (001) substrate, determining the composition, studying structural properties, relaxation mechanisms and surface morphology are presented. Using pulsed laser deposition, epitaxial growth of the Ga1-yInyAs1-xBix thin film was carried out on the Si (001) substrate. Using X-ray diffraction, it was established that the Ga1-yInyAs1-xBix film was grown with a large lattice mismatch (Δa/a = 7.838 %). It is shown that the film has a well-pronounced texture in the [001] growth direction, a lattice parameter of 5.856 Å. Using Medium Energy Ion Scattering, a decrease in the In concentration after a layer thickness ≈15 nm from 0.5 to 0.4 mol frac. was detected. An important result is the homogeneous distribution of Bi throughout the layer thickness. Structural studies allow for the conclusion that stress relaxation occurred because of shears by means of a nucleation of dislocations and a slip close-packed {111} planes, as well as twinning, which led to a change in composition after a thickness of ≈15 nm from the substrate and an increase in the surface roughness of the layer.

Surface ionic coordination of Al2O3–CaO–based molten slag induced by structural relaxation

AbstractThe surface tensions of molten oxides depend strongly on the structural relaxation of the surface region. The mechanism of surface structural relaxation for molten oxide slags is complex. The surface tension of calcium aluminate slag is minimal at an intermediate composition, although the critical reason has not been identified. Here, two novel approaches were used to evaluate the features of surface ionic structures in the molten state for the range of 25–50 mol% Al2O3: (1) X‐ray absorption analysis of oxygen and cationic elements in glass samples after surface relaxation treatment, and (2) molecular dynamics simulations, based on a polarizable‐ion model, of the ionic distribution in a molten slag with vacuum/melt interfaces. The results indicate that bridging oxygen (BO) ions are preferred to non‐BOs in the surface region. In calcium aluminate slag, BOs are formed by connecting two AlO4 tetrahedrons with charge compensation of two Al3+ ions with one Ca2+ ion. Additionally, the above approaches were used to qualify the effect on the surface ionic structure of adding 1–20 mol% SiO2 to the calcium aluminate slag. The results indicated that the SiO4 tetrahedrons incorporate the vertex connection with AlO4 tetrahedrons to form BOs in the surface region.

Drift of Schottky Barrier Height in Phase Change Materials.

Phase-change memory (PCM) devices have great potential as multilevel memory cells and artificial synapses for neuromorphic computing hardware. However, their practical use is hampered by resistance drift, a phenomenon commonly attributed to structural relaxation or electronic mechanisms primarily in the context of bulk effects. In this study, we reevaluate the electrical manifestation of resistance drift in sub-100 nm Ge2Sb2Te5 (GST) PCM devices, focusing on the contributions of bulk vs interface effects. We employ a combination of measurement techniques to elucidate the current transport mechanism and the electrical manifestation of resistance drift. Our steady-state temperature-dependent measurements reveal that resistance in these devices is predominantly influenced by their electrical contacts, with conduction occurring through thermionic emission (Schottky) at the contacts. Additionally, temporal current-voltage characterization allows us to link the resistance drift to a time-dependent increase in the Schottky barrier height. These findings provide valuable insights, pinpointing the primary contributor to resistance drift in PCM devices: the Schottky barrier height for hole injection at the interface. This underscores the significance of contacts (interface) in the electrical manifestation of drift in PCM devices.

Atomistic mechanism of structural and volume relaxation below glass transition temperature in a soda-lime silicate glass revealed by Raman spectroscopy and its DFT calculations.

To elucidate the atomistic origin of volume relaxation in soda-lime silicate glass annealed below the glass transition temperature (Tg), the experimental and calculated Raman spectra were compared. By decomposing the calculated Raman spectra into specific groups of atoms, the Raman peaks at 800, 950, 1050, 1100, and 1150cm-1 were attributed to oxygen and silicon in Si-O-Si, non-bridging oxygen in the Q2 unit, bridging oxygen in low-angle Si-O-Si, non-bridging oxygen in the Q4 unit, and bridging oxygen in high-angle Si-O-Si, respectively. Based on these attributions, we found that by decreasing the fictive temperature by annealing below Tg - 70K, a homogenization reaction Q2 + Q4 → 2Q3 and an increase in average Si-O-Si angle occurred simultaneously. By molecular dynamics simulation, we clarified how the experimentally demonstrated increase in average Si-O-Si angle contributes to volume shrinkage; increasing Si-O-Si angles can expand the space inside the rings, and Na can be inserted into the ring center.

Structural study and temperature dependent relaxation and conduction mechanism of orthorhombic tungsten bronze Ba4La28/3(Zr0.05Ti0.95)18O54 ceramic

In this study, the Ba4La28/3(Zr0.05Ti0.95)18O54 ceramic was prepared using the solid-state technique. The X-ray diffraction technique was used in this study to investigate the Ba/La order in the solid solution Ba4La28/3(Zr0.05Ti0.95)18O54. We have developed a structural model, to represent the order within the structure. The formula of model [Ba4−a□a]A2[La8+2b3□2−2b3]A1,A1′(Zr0.05Ti0.95)18O54 is described as perovskite layers with a thickness of 3 octahedral parallel to the xOz plane. Scanning electron microscopy (SEM) showed that Ba4La28/3(Zr0.05Ti0.95)18O54 ceramic exhibits a typical columnar grain with a heterogeneous distribution over the entire surface. Complex impedance spectroscopy was used to analyze the dielectric and electrical properties of Ba4La28/3(Zr0.05Ti0.95)18O54 materials over a frequency range of 10 Hz to 1 MHz and a temperature range of 350°C to 400°C. An appropriate equivalent electrical circuit was also used to investigate the contributions of grains and grain boundaries. The AC-conductivity data was analyzed using Jonscher's universal power law. The thermal behavior of the exponent parameter "s" indicates that the dominant conduction mechanism in our compound is the non-overlapping small polaron tunneling (NSPT) model. The activation energies calculated from the conduction and relaxation mechanisms are nearly identical for the Ba4La28/3(Zr0.05Ti0.95)18O54 ceramic.

Experimental and constitutive analyses of the stress relaxation behavior of glassy polymers

AbstractThe physical mechanism underlying the mechanical behavior of glassy polymers has been studied over decades but remains a long‐standing issue. A consensus view achieved is that the yield, flow, and stress relaxation behaviors are due to structural relaxation in the polymer mainly caused by chain conformation transitions. This is the key physical idea behind the many existing elastic–plastic constitutive models for glassy polymers. In this paper, such a constitutive model was employed for predicting and analyzing the stress relaxation of a glassy polymer. It is found that the model works well in predicting the pre‐yield stress relaxation but significantly underestimates the post‐yield stress relaxation. As considering the chain conformation transition alone leads to a dilemma for the model to concurrently represent the yield/flow and stress relaxation behaviors, the model was extended to incorporate an additional structural relaxation mechanism assumed to originate from the dissociation of weak linkages in the chain network. The extended model succeeds in concurrently representing the yield/flow, and stress relaxation behaviors in the whole deformation region, of which the reasons were analyzed. The knowledge revealed in this paper is instructive and may shed new light on understanding the structural relaxation and mechanical behavior of glassy polymers.

Metastable states, relaxation and failure mechanisms in condensed matter with defects

The article is concerned with experimental studies of anomalous momentum transfer mechanisms in condensed matter exhibiting multiple defect-induced gaped momentum states. The performed experiments revealed the relationship between the metastable states, the specific critical phenomena in condensed matter with defects, the structural-scaling transitions, and the mechanisms of structural relaxation disclosing viscosity anomalies in solids and liquids due to the strong interactions between the structure constituents. The possibility of these mechanisms under intensive loading including turbulence was substantiated in Naimark (1998), Naimark (1997), Naimark (2004). The established regularities of criticality in the behavior of condensed matter with mesoscopic defects made it possible to study the thermodynamics and kinetics of the nonlinear liquid and solid systems exhibiting the metastable states, and to provide an explanation of the anomalous mechanisms of momentum transfer in systems with "strong interaction." Anomalous momentum transfer mechanisms are associated with the subjection of the dynamics of condensed matter to the established types of collective modes in ensembles of defects (breathers, autosolitons, dissipative blow-up structures) manifesting the character of self-similar solutions. The subordination of dynamics to collective modes is accompanied by a sharp increase in the effective relaxation times and absorption anomalies. The theoretical results are confirmed by the experimental data on the formation of self-similar (quasi-plastic) fronts in liquids and the attainment of viscosity asymptotics due to initiation of fracture waves under shock-wave loading of fused quartz (Naimark (2003), Naimark (2010)).

Parameterization of photobleaching and photodarkening in-situ kinetics in thermally deposited GeSe2 thin films

Thermally evaporated chalcogenide glass thin films are known to be highly photosensitive revealing both metastable and transient photoinduced changes of optical transmission at the fundamental absorption edge region. In-situ kinetics of metastable photobleaching and transient photodarkening as well as following light-off relaxations for as-deposited GeSe2 thin films were studied and fitted with the stretched exponential function. Dependences of kinetic parameters β and τ on film thickness, temperature, sample prehistory and wavelength of light irradiation were analyzed. The obtained results were discussed within current approaches to mechanisms of photoinduced kinetic phenomena and structural relaxation in glasses.

Molecular dynamics simulations vs field-cycling NMR relaxometry: Structural relaxation mechanisms in the glass-former glycerol revisited.

We combine field-cycling (FC) relaxometry and molecular dynamics (MD) simulations to study the rotational and translational dynamics associated with the glassy slowdown of glycerol. The 1H NMR spin-lattice relaxation rates R1(ω) probed in the FC measurements for different isotope-labelled compounds are computed from the MD trajectories for broad frequency and temperature ranges. We find high correspondence between experiment and simulation. Concerning the rotational motion, we observe that the aliphatic and hydroxyl groups show similar correlation times but different stretching parameters, while the overall reorientation associated with the structural relaxation remains largely isotropic. Additional analysis of the simulation results reveals that transitions between different molecular configurations are slow on the time scale of the structural relaxation at least at sufficiently high temperatures, indicating that glycerol rotates at a rigid entity, but the reorientation is slower for elongated than for compact conformers. The translational contribution to R1(ω) is well described by the force-free hard sphere model. At sufficiently low frequencies, universal square-root laws provide access to the molecular diffusion coefficients. In both experiment and simulation, the time scales of the rotational and translational motions show an unusually large separation, which is at variance with the Stokes-Einstein-Debye relation. To further explore this effect, we investigate the structure and dynamics on various length scales in the simulations. We observe that a prepeak in the static structure factor S(q), which is related to a local segregation of aliphatic and hydroxyl groups, is accompanied by a peak in the correlation times τ(q) from coherent scattering functions.

Steady plastic wave fronts and scale universality of strain localization in metals and ceramics

Mechanisms of structural relaxation are linked with the metastability of nonequilibrium potential of solid with defects and the generation of collective modes of defects responsible for the plastic strain and damage localization. It is shown that spatial-temporal dynamics of collective modes (auto-solitary and blow-up dissipative structures) provide the anomalous relaxation ability of nonlinear system “solid with defects” in the conditions of the specific type of criticality – structural-scaling transition. These modes have the nature of self-similar solutions of evolution equations for damage parameter (defect-induced strain) and represent the “universality class” providing the four power law for a steady plastic front, splitting of an elastoplastic shock wave front, and elastic precursor decay kinetics. Wide-range constitutive equations reflecting the linkage between defect-induced mechanisms and structural relaxation are used in the numerical simulation for shock wave loading of metals and ceramics in the comparison with experiments.

Critical Phenomena in Portevin–Le Chatelier effect during compression of aluminium-magnesium alloy and stored energy evolution

This work was inspired by works of Gianfranco D’Anna (2000) where the Portevin-Le Chaˆtelier effect (PLC) was investigated by compressing Al-Mg alloy specimen in a very large deformation range and the results were interpreted from the viewpoint of phase transitions and critical phenomena. Two critical points where deformation process changes from “laminar” to jerky flow and back were noticed. We found that the second critical point where the rate of the serrations is decreased before the macroscopic fracture is not reachable for some alloys even with proposed geometry. We have tested 2 sets of specimens made of the same AMG6 alloy (~6% of magnesium) but with different amount of Si obtained from different producers. Specimens with a higher amount of Si tends to fracture before reaching the second point.Also, we have measured the amount of stored energy which can be recovered as heat during the annealing process. We used the differential scanning calorimeter STA "Jupiter" 449. We found that the amount of this energy sharply increases with the beginning of PLC serrations (first critical point) and drops at a second critical point or at macroscopic fracture. This can be related to a special type of critical phenomena—structural scaling transitions in mesodefect ensembles and associated structural relaxation mechanisms Naimark (2016)

Numerical Simulation and Experimental Study of Plastic Strain Localization under the Dynamic Loading of Specimens in Conditions Close to a Pure Shear

Mechanisms of plastic strain localization under the dynamic loading of specially shaped specimens made of the AMg6 aluminum alloy and intended for tests under conditions close to a pure shear on a split Hopkinson–Kolsky pressure bar are studied theoretically and experimentally. The mechanisms of plastic flow instability are related to collective effects in the ensemble of microdefects in spatially localized regions visualized in situ using a CEDIP Silver 450M high-speed infrared camera. The calculation corresponding to the experimental loading scheme is implemented using wide range constitutive equations reflecting the dependence of structural relaxation mechanisms—manifestation of the collective behavior of microdefects—on the evolution of the localized flow shear instability. Microstructure analysis of deformed specimens included the study of the spatial relief (porosity) scaling by the data of a NewView-5010 microscope-interferometer in regions of plastic strain localization. An increase in the structural scaling exponent (Hurst exponent) reflected the degree of the multiscale correlated behavior of defects and the porosity induced by them in regions of localized plasticity. Infrared scanning of the strain localization region and numerical simulation followed by an estimate of the defect structure corroborated the hypothesis that effects of thermal softening do not play a decisive role in the process of plastic shear localization in the tested material under the considered loading regimes. A new, one of the possible ones, mechanism of plastic strain localization under dynamic loading is justified. It is caused by the multiscale collective behavior of mesodefects—structure-scaling transitions—and establishes the stadiality of the localized shear evolution.

A thermoviscoelastic model incorporated with uncoupled structural and stress relaxation mechanisms for amorphous shape memory polymers

In this paper, a thermoviscoelastic constitutive model incorporating uncoupled structure and stress relaxation is proposed to capture the material behavior for thermally induced amorphous shape memory polymers. The leading particulars of this model is that the structure and stress relaxation mechanisms are not coupled but connected by the internal state variable which describes the degree of volume departure from equilibrium. Based on the internal variable, a simplified KAHR model is developed for the structure relaxation, and a new relaxation time model is proposed to describe the temperature and structure dependence of the characteristic stress relaxation. Moreover, the Eying model is modified by the new stress relaxation model to study the stress-activated viscous flow. Finally, the thermoviscoelastic constitutive model is applied to investigate the shape recovery behavior and the yielding and post-yielding behavior, and the simulation results show good agreement with the experimental data.

Structural relaxation mechanisms in hydrous sodium borosilicate glasses

Borosilicate glasses (16Na2O–10B2O3–74SiO2, NBS) with water contents up to 22 mol% H2O were prepared to study the effect of water on structural relaxation using DTA, viscometry and internal friction measurements. The results show that the glass transition temperature Tg of DTA and the isokom temperature T12, of viscometry are in excellent agreement, confirming the equivalence of enthalpy and viscous relaxation for NBS glass. Combining Tg data with water speciation data demonstrates that OH groups are mainly responsible for the decrease of Tg with increasing hydration, while molecular water plays only a minor role. Internal friction spectra at 7.125 Hz confirm the decisive influence of water on mechanical relaxation. The temperature range of α-relaxation (glass transition) strongly decreases while two β-relaxation peaks (sub-Tg) progressively appear with increasing water content. A high temperature β-relaxation peak, attributed to the presence of OH groups, shifts from 670 to 450 K as total water content increases from 0.01 to 5 wt%. A low temperature β-relaxation peak, attributed to molecular water, appears at 380 K and 330 K in glasses containing 3 and 5 wt% H2O, respectively. These findings suggest that relaxation mechanism of different hydrous species at low temperature may contribute to fatigue of stressed glasses.

Metastable states, relaxation mechanisms, and fracture of liquids under severe loading conditions

The relaxation properties and fracture of glycerol, silicone oil, transformer oil, and water have been studied experimentally under shock wave loading. The power-law strain rate dependences of the stress amplitude and spall strength were found for the compression and rarefaction fronts, respectively. It was shown that temperature has a strong influence on the spall strength of glycerol near the phase transformation temperature. The power laws reflect a self-similar nature of the momentum transfer and fracture mechanisms of liquids that are conventionally observed in solids and governed by the mechanisms of defect-induced structural relaxation. The mechanisms of viscoelasticity are related to the metastable states that may give rise to a collective behavior of displacement field fluctuations (microshearing) in liquids and thus provide a viscoplastic response of liquids under high strain rate loading.

Structural and Dielectric Relaxations in Vitreous and Liquid State of Monohydroxy Alcohol at High Pressure.

2-Ethyl-1-hexanol monoalcohol is a well-known molecular glassformer, which for a long time attracts attention of researchers. As in all other monohydroxy alcohols, its dielectric relaxation reveals two distinct relaxation processes attributed to the structural relaxation and another more intense process, which gives rise to a low-frequency Debye-like relaxation. In this monoalcohol, the frequency separation between these two processes reaches an extremely high value of 3 orders of magnitude, which makes this substance a rather convenient object for studies of mechanisms (supposedly common to all monoalcohols) leading to vitrification of this type of liquids. In this work, we apply two experimental techniques, dielectric spectroscopy and ultrasonic measurements (in both longitudinal and transverse polarizations) at high pressure, to study interference between different relaxation mechanisms occurring in this liquid, which could shed light on both structural and dielectric relaxation processes observed in a supercooled liquid and a glass state. Application of high pressure in this case leads to the simplification of the frequency spectrum of dielectric relaxation, where only one asymmetric feature is observed. Nonetheless, the maximum attenuation of the longitudinal wave in ultrasonic experiments at high pressure is observed at temperatures ≈50 K above the corresponding temperature for the transverse wave. This might indicate different mechanisms of structural relaxation in shear and bulk elasticities in this liquid.

Reversible plasticity shape memory effect in epoxy/CNT nanocomposites - A theoretical study

A theoretical investigation on the reversible plasticity shape memory (RPSM) properties of Multi-Walled Carbon Nanotubes (MWCNT) reinforced epoxy nanocomposites is presented. A typical RPSM cycle involves loading and stress relaxation below the glass transition temperature and unconstrained strain recovery above glass transition temperature. This paper attempts to study the underlying mechanisms by employing a thermo-visco-elastic model incorporating structural and stress relaxation mechanisms. The effective properties of the nanocomposites were determined from basic micro-mechanics models and standard thermo-mechanical experiments. The variations in model parameters between neat and filled epoxy were studied and the influence of MWCNT on the material behavior are discussed. The simulations agreed quite well with the experimental results for both neat and filled epoxy. The model was further able to capture the thermo-mechanical behavior under different programming conditions like strain rate, strain level and relaxation time.

Multiscale structural relaxation and adiabatic shear failure mechanisms

Stages of plastic shear instability and adiabatic shear failure are associated with the initiation of collective modes of defect ensembles that have a self-similar nature of autosoliton and "blow-up" structures. Experimental and structural studies have confirmed simulation results for the stages of plastic strain localization and adiabatic shear failure based on the constitutive equations that relate structural relaxation and failure mechanisms to the formation of multiscale collective modes in defect ensembles.

Collective properties of defects, multiscale plasticity, and shock induced phenomena in solids

A statistically based approach is developed for the construction of constitutive equations that provides linkages between defect-induced mechanisms of structural relaxation, thermally activated plastic flow, and material response to extreme loading conditions. The collective properties of defects have been studied to establish the interaction of multiscale defect dynamics and plastic flow, and to explain the mechanisms leading to the universal self-similar structure of shock wave fronts. Pn explanation for structural universality of the steady-state plastic shock front (the four power law) and the self-similarity of shock wave profiles under reloading (unloading) is proposed. Structural characterization under transition from thermally activated dislocation glide to nonlinear dislocation drag effects is developed in terms of scaling invariants (effective temperatures) related to mesodefect induced morphology formed during the different stages of plastic deformation.

Studying plastic shear localization in aluminum alloys under dynamic loading

An experimental and theoretical study of plastic shear localization mechanisms observed under dynamic deformation using the shear–compression scheme on a Hopkinson–Kolsky bar has been carried out using specimens of AMg6 alloy. The mechanisms of plastic shear instability are associated with collective effects in the microshear ensemble in spatially localized areas. The lateral surface of the specimens was photographed in the real-time mode using a CEDIP Silver 450M high-speed infrared camera. The temperature distribution obtained at different times allowed us to trace the evolution of the localization of the plastic strain. Based on the equations that describe the effect of nonequilibrium transitions on the mechanisms of structural relaxation and plastic flow, numerical simulation of plastic shear localization has been performed. A numerical experiment relevant to the specimen-loading scheme was carried out using a system of constitutive equations that reflect the part of the structural relaxation mechanisms caused by the collective behavior of microshears with the autowave modes of the evolution of the localized plastic flow. Upon completion of the experiment, the specimens were subjected to microstructure analysis using a New View-5010 optical microscope–interferometer. After the dynamic deformation, the constancy of the Hurst exponent, which reflects the relationship between the behavior of defects and roughness induced by the defects on the surfaces of the specimens is observed in a wider range of spatial scales. These investigations revealed the distinctive features in the localization of the deformation followed by destruction to the script of the adiabatic shear. These features may be caused by the collective multiscale behavior of defects, which leads to a sharp decrease in the stress-relaxation time and, consequently, a localized plastic flow and generation of fracture nuclei in the form of adiabatic shear. Infrared scanning of the localization zone of the plastic strain in situ and the subsequent study of the defect structure corroborated the hypothesis about the decisive role of non-equilibrium transitions in defect ensembles during the evolution of a localized plastic flow.